Low density polyolefin resins with high dimensional stability

ABSTRACT

The present disclosure generally relates to low density compositions useful for making automotive components, such as molded parts, as well as other articles of manufacture; such compositions comprise (a) a polyolefin comprising polypropylene, a propylene-ethylene block copolymer, or combinations thereof, wherein the polyolefin blend is present in an amount ranging from about 53 wt. % to about 65 wt. %, based on a total weight of the composition; (b) a first elastomer, a second elastomer, and an impact-modifying compatibilizer, wherein the combined weight percent of components (b) ranges from about 27 wt. % to about 32 wt. %, based on the total weight of the composition; (c) a filler present in an amount ranging from about 5 wt. % to about 12 wt. %, based on the total weight of the composition; and (d) an additive package present in an amount ranging from about 0.5 wt. % to about 5 wt. %.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. ProvisionalApplication No. 62/363,729, filed Jul. 18, 2016, the contents of whichare incorporated herein by reference in their entirety.

BACKGROUND Field of the Invention

In general, the present disclosure relates to the field of chemistry.More specifically, the present disclosure relates to polyolefin-basedcompositions. In some embodiments, the polyolefin-based compositionsdisclosed herein are useful as components for automobiles and otherproducts, including injection molded parts.

Description of Related Art

The global automotive industry is seeking weight reduction for manycomponents used to make vehicles in order to comply with increased fuelefficiency goals and other environmentally important standards (e.g.,Corporate Average Fuel Economy (CAFE) in US, CO₂ limits in the EuropeanUnion (E.U.)). Automotive components made from polyolefin-basedcompositions include spare-wheel compartment covers, underbody panels,seat backrests, engine and transmission covers, bumper fascia, rearpanel shelves, and door trim panels. It would be desirable to achieveweight reductions in the polyolefin-based compositions (resins) used tomake injection molded parts without compromising critical propertiesrelated to fit and function, including the compositions' coefficient oflinear thermal expansion (CLTE), shrinkage, gap closure, etc. Challengesabound, as reducing, for example, higher weight filler content of apolyolefin-based composition may result in a disadvantageous increase inCLTE, shrinkage and/or panel gap.

SUMMARY OF THE INVENTION

In one aspect, the present disclosure provides for a compositioncomprising: (a) a polyolefin comprising polypropylene, apropylene-ethylene block copolymer, or combinations thereof, wherein thepolyolefin is present in an amount ranging from about 53 wt. % to about65 wt. %, based on a total weight of the composition; (b) a firstelastomer, a second elastomer, and an impact-modifying compatibilizer,wherein the combined weight percent of the first elastomer, the secondelastomer, and the impact-modifying compatibilizer ranges from about 25wt. % to about 34 wt. %, based on the total weight of the composition;(c) a filler present in an amount ranging from about 5 wt. % to about 12wt. %, based on the total weight of the composition; and (d) an additivepackage present in an amount ranging from about 0.5 wt. % to about 5 wt.%, based on the total weight of the composition; wherein the compositionhas a density ranging from about 0.90 to about 1.00 g/cm³, anafter-bake-mold-shrinkage (0.5 hours, 120° C.) ranging from about 0.5percent to about 0.9 percent, a coefficient of linear thermal expansionranging from about 1 to about 8 (10E−5 mm/mm/° C.), and a flexuralmodulus between about 1,200 MPa and about 2,500 MPa.

The present disclosure further describes articles that may be used asparts for automobiles, water vessels, locomotives, recreationalvehicles, or airplanes, which comprise compositions comprising: (a) apolyolefin comprising polypropylene, a propylene-ethylene blockcopolymer, or combinations thereof, wherein the polyolefin is present inan amount ranging from about 53 wt. % to about 65 wt. %, based on atotal weight of the composition; (b) a first elastomer, a secondelastomer, and an impact-modifying compatibilizer, wherein the combinedweight percent of the first elastomer, the second elastomer, and theimpact-modifying compatibilizer ranges from about 25 wt. % to about 34wt. %, based on the total weight of the composition; (c) a fillerpresent in an amount ranging from about 5 wt. % to about 12 wt. %, basedon the total weight of the composition; and (d) an additive packagepresent in an amount ranging from about 0.5 wt. % to about 5 wt. %,based on the total weight of the composition; wherein the compositionhas a density ranging from about 0.90 to about 1.00 g/cm³, anafter-bake-mold-shrinkage (0.5 hours, 120° C.) ranging from about 0.5percent to about 0.9 percent, a coefficient of linear thermal expansionranging from about 1 to about 8 (10E−5 mm/mm/° C.), and a flexuralmodulus between about 1,200 MPa and about 2,500 MPa.

While multiple embodiments are disclosed, still other embodiments willbecome apparent to those skilled in the art from the following detaileddescription. As will be apparent, certain embodiments, as disclosedherein, are capable of modifications in various aspects, all withoutdeparting from the spirit and scope of the claims as presented herein.Accordingly, the drawings and detailed description are to be regarded asillustrative in nature and not restrictive.

DETAILED DESCRIPTION OF THE INVENTION

Provided herein are polyolefin-based compositions useful as componentsfor automobiles, water vessels, locomotives, recreational vehicles,airplanes and other products, including, for example, injection moldedparts. In some embodiments, these compositions (resins) allow for thepreparation of injection molded parts having a reduced density whilemaintaining or improving one or more of the following properties of ahigher density resin: CLTE, low shrinkage, and dimensional stability.

In one aspect of the present disclosure, there are provided compositionscomprising:

-   (a) a polyolefin comprising a polypropylene, a propylene-ethylene    block copolymer, or combinations thereof, wherein the polyolefin is    present in an amount ranging from about 53 wt. % to about 65 wt. %,    based on a total weight of the composition;-   (b) a first elastomer, a second elastomer, and an impact-modifying    compatibilizer, wherein the combined weight percent of the first    elastomer, the second elastomer, and the impact-modifying    compatibilizer ranges from about 25 wt. % to about 34 wt. %, based    on the total weight of the composition;-   (c) a filler present in an amount ranging from about 5 wt. % to    about 12 wt. %, based on the total weight of the composition; and-   (d) an additive package present in an amount ranging from about 0.5    wt. % to about 5 wt. %, based on the total weight of the    composition;    wherein the composition has a density ranging from about 0.90 to    about 1.00 g/cm³, an after-bake-mold-shrinkage (0.5 hours, 120° C.)    ranging from about 0.5 percent to about 0.9 percent, a coefficient    of linear thermal expansion ranging from about 1 to about 8 (10E−5    mm/mm/° C.), and a flexural modulus between about 1,200 MPa and    about 2,500 MPa.

In some embodiments, the composition has a melt flow rate (MFR, ASTMD1238, 230° C., 2.16 kg) from about 15 g/10 min to about 50 g/10 min;alternatively from about 20 g/10 min to about 50 g/10 min; andalternatively from about 15 g/10 min to about 35 g/10 min.

In some embodiments, the composition has a density from about 0.90 g/cm³to about 0.97 g/cm³. In some of these embodiments, the composition has adensity from about 0.94 g/cm³ to about 0.96 g/cm³.

In some embodiments, the composition has a coefficient of linear thermalexpansion (CLTE) from about 1 (10⁻⁵ mm/mm/° C.) to about 8 (10⁻⁵ mm/mm/°C.); alternatively from about 2 (10⁻⁵ mm/mm/° C.) to about 8 (10⁻⁵mm/mm/° C.); alternatively from about 3 (10⁻⁵ mm/mm/° C.) to about 8(10⁻⁵ mm/mm/° C.); alternatively from about 5 (10⁻⁵ mm/mm/° C.) to about8 (10⁻⁵ mm/mm/° C.); alternatively from about 5.5 (10⁻⁵ mm/mm/° C.) toabout 6.5 (10⁻⁵ mm/mm/° C.).

In some embodiments, the composition has a Charpy notched impactstrength at 23° C. from about 25 kJ/m² to about 60 kJ/m². In some ofthese embodiments, the Charpy notched impact strength at 23° C. is fromabout 25 kJ/m² to about 50 kJ/m². In some of these embodiments, theCharpy notched impact strength at 23° C. is from about 28 kJ/m² to about50 kJ/m². In some embodiments, the composition has a Charpy notchedimpact strength at 0° C. ranging from about 5 kJ/m² to about 35 kJ/m².In some of these embodiments, the composition has a Charpy notchedimpact strength at −40° C. from about 2 kJ/m² to about 5 kJ/m².

In some embodiments, the composition has a flexural modulus betweenabout 1,500 MPa and about 2,200 MPa; alternatively between about 1,600MPa and about 2,000 MPa; and alternatively between about 1650 MPa andabout 2,100 MPa.

In some embodiments, the as-molded shrinkage (“AMMS”) of the compositionis ≦0.6%. In some embodiments, the as-molded shrinkage of thecomposition is from about 0.4% to about 0.8%. In some embodiments, theafter-bake shrinkage of the composition is ≦0.8%. In some embodiments,the as-molded shrinkage of the composition is from about 0.5% to about1.2%. In accordance with some embodiments of the present disclosure, theas-molded shrinkage may be measured using a modified ISO-294-4 method,wherein the method was modified by molding a 4×6×⅛ inch plaquecomprising the composition, allowing the plaque to cool to roomtemperature and re-condition for over 24 hours, and measuring theaverage shrinkage utilizing a fixed gauge.

In some embodiments, the after-bake-mold-shrinkage (“ABMS”) (0.5 hours,120° C.) of the composition ranges from about 0.5% to about 1.0%,alternatively from about 0.6% to about 1.0%; alternatively from about0.6% to about 0.9%; and alternatively from about 0.6% to about 0.8%. Theafter-bake-mold-shrinkage may be measured using a modified ISO-294-4method, wherein the method was modified by molding a 4×6×⅛ inch plaqueof the sample composition to a set temperature of 120° C. for either anhour or a half hour (as indicated), and measuring the average shrinkageafter it is returned to room temperature and re-conditioned (i.e.,allowed to stabilize by leaving it at room temperature and a controlledhumidity for over 24 hours) utilizing a fixed gauge.

I. Polyolefin

In some embodiments, the polyolefin is present in an amount ranging fromabout 55 wt. % to about 63 wt. %, based on the total weight of thecomposition. In some of these embodiments, the polyolefin is present inan amount of about 59 wt. %, based on the total weight of thecomposition. In some embodiments, the polyolefin comprises apolypropylene having high crystallinity homopolymer portions. “Highcrystallinity” refers to polypropylene with a percentage of mesopentadgreater than 97% mmmm, as determined by high field NMR. See for example,WIPO PCT Patent Application Publication No. WO 2009/045351, which isincorporated herein by reference. In some of these embodiments, thepolyolefin has a melt flow rate (MFR, ASTM D1238, 230° C., 2.16 kg) fromabout 40 g/10 min to about 90 g/10 min; alternatively from about 50 toabout 80 g/10 min; alternatively from about 55 to about 75 g/10 min;alternatively from about 60 to about 70 g/10 min; and alternativelyabout 65 g/10 min.

In alternative embodiments, the polyolefin is a blend of two or morepolypropylene homopolymers, or propylene-ethylene copolymers, orpropylene-ethylene block copolymers, or one or more polypropylenehomopolymer and one or more propylene-ethylene copolymers orpropylene-ethylene block copolymers. In the alternative embodiment, thetotal polyolefin is present in an amount ranging from about 55 wt. % toabout 63 wt. %, based on a total weight of the composition. In some ofthese embodiments, the total polyolefin is present in an amount of about59 wt. %, based on a total weight of the composition. In some of theseembodiments, the blended polyolefin has a combined melt flow rate (MFR,ASTM D1238, 230° C., 2.16 kg) of from about 40 g/10 min to about 90 g/10min; alternatively from about 50 to about 80 g/10 min; alternativelyfrom about 55 to about 75 g/10 min; alternatively from about 60 to about70 g/10 min; and alternatively about 65 g/10 min. Accordingly,polyolefins having melt flow rates higher than those disclosed herein orlower than those disclosed herein may be utilized in order to obtain ablended polyolefin having an overall melt flow rate (MFR, ASTM D1238,230° C., 2.16 kg) from about 40 g/10 min to about 90 g/10 min;alternatively from about 50 to about 80 g/10 min; alternatively fromabout 55 to about 75 g/10 min; alternatively from about 60 to about 70g/10 min; and alternatively about 65 g/10 min.

Suitable polyolefins include commercially available polypropylenes,including without limitation ADSTIF™, METOCENE™, and PROFAX™, eachavailable from LyondellBasell Industries (Houston, Tex., USA).

II. Elastomers

In some embodiments, the elastomers of the compositions provided hereinhave the following properties and are present in the amounts indicatedbelow:

-   (i) the first elastomer comprises an ethylene-based copolymer having    a density from about 0.87 g/cm³ to about 0.90 g/cm³, wherein the    first elastomer is present in an amount ranging from about 10 wt. %    to about 22 wt. %, based on the total weight of the composition;-   (ii) a second elastomer comprising an ethylene-based copolymer    having a density from about 0.85 g/cm³ to about 0.87 g/cm³, wherein    the second elastomer is present in an amount ranging from about 4    wt. % to about 15 wt. %, based on the total weight of the    composition; and-   (iii) an impact-modifying compatibilizer, wherein the    impact-modifying compatibilizer is present in an amount ranging from    about 0.5 wt. % to about 8 wt. %, based on the total weight of the    composition;    such that the combined weight percent of the first elastomer, the    second elastomer, and the impact-modifying compatibilizer ranges    from about 25 wt. % to about 34 wt. %, alternatively from about 27    wt. % to about 32 wt. %, based on the total weight of the    composition.

In some embodiments, the ethylene-based copolymer of the first elastomeris present in an amount ranging from about 12 wt. % to about 20 wt. %,alternatively from about 16 wt. %, based on the total weight of thecomposition. In some embodiments, the ethylene-based copolymer of thefirst elastomer has a melt flow rate (190° C., 2.16 kg) from about 0.4g/10 min to about 1.1 g/10 min; alternatively from about 0.6 g/10 min toabout 0.9 g/10 min. In some embodiments, the ethylene-based copolymer ofthe first elastomer is an ethylene-butene copolymer, ethylene-hexenecopolymer, or an ethylene-octene copolymer.

In some embodiments, the ethylene-based copolymer of the secondelastomer is present in an amount ranging from about 6 wt. % to about 12wt. %; alternatively about 9 wt. %, based on the total weight of thecomposition. In some embodiments, the ethylene-based copolymer of thesecond elastomer has a melt flow rate (190° C., 2.16 kg) from about 1.0g/10 min to about 1.5 g/10 min, for example, a melt flow rate of about1.2 g/10 min. In some embodiments, the ethylene-based copolymer of thesecond elastomer is an ethylene-butene copolymer.

In alternative embodiments, the ethylene-based copolymer of the secondelastomer has a melt flow rate (190° C., 2.16 kg) ranging from about 5g/10 min to about 50 g/10 min; alternatively from about 10 g/10 min toabout 40 g/10 min; alternatively from about 10 g/10 min to about 15 g/10min; alternatively about 13 g/10 min; alternatively from about 25 g/10min to about 35 g/10 min; alternatively about 30 g/10 min. In someembodiments, the ethylene-based copolymer of the second elastomer is anethylene-octene copolymer.

In some embodiments, an impact-modifying compatibilizer for use with thepresent disclosure may be a styrene-ethylene-butylene-styrene (SEBS)rubber or a heterophasic polypropylene copolymer. In an embodiment, theimpact-modifying compatibilizer may be present in an amount ranging fromabout 1 wt. % to about 10 wt. %; alternatively from about 2 wt. % to 8wt. %; alternatively from about 4 wt. % to about 6 wt. %; andalternatively about 4 wt. %, based on the total weight of thecomposition. In some embodiments, the styrene-ethylene-butylene-styrene(SEBS) rubber of the impact-modifying compatibilizer has a melt flowrate (230° C., 5.0 kg) ranging from about 15 g/10 min to about 33 g/10min, for example, a melt flow rate of about 22 g/10 min. In someembodiments, polyolefin heterophasic copolymer of the impact-modifyingcompatibilizer has a melt flow rate (230° C., 2.16 kg) ranging fromabout from about 0.1 g/10 min to about 2 g/10 min, alternatively from0.35 g/10 min to 1 g/10 min, alternatively about 0.45 g/10 min.

In an embodiment, the heterophasic polypropylene copolymer of theimpact-modifying compatibilizer comprises:

-   -   a) from 30-80 wt. % (alternatively from 30-70 wt. %;        alternatively from about 45 wt. % to about 55 wt. %) of a        semi-crystalline polypropylene component (Component A) having a        monomodal molecular weight distribution selected from the group        consisting of a propylene homopolymer, a random copolymer of        propylene containing up to 8% of ethylene, a random copolymer of        propylene containing up to 8% of at least one C₄-C₁₀ α-olefin,        and any combination thereof; optionally the semi-crystalline        polypropylene may have a melt flow rate (MFR) of from 1 g/10 min        to 500 g/10 min; and    -   b) from 20-70 wt. % (alternatively from 40-70 wt. %;        alternatively from about 45 wt. % to about 55 wt. %) of a        bipolymer component (Component B) of propylene and at least one        comonomer selected from ethylene and/or C₄-C₁₀ α-olefins, the        bipolymer containing from 50-75% of propylene, wherein the        bipolymer is soluble in xylene at room temperature and has an        intrinsic viscosity [η] of from 4 to 7.5 dl/g (in decalin);        optionally Component B is soluble in xylene at room temperature        and has from 25 wt % to about 50 wt %, alternatively from about        30 wt % to about 45 wt %, ethylene moieties and an intrinsic        viscosity [η] at room temperature of 4-7 dL/g (in decalin); and        optionally Component B has a melt flow rate less than 0.15 g/10        min.

In some embodiments, the combined weight percent of the first elastomer,the second elastomer, and the impact-modifying compatibilizer rangesfrom about 25 wt. % to about 34 wt. %, alternatively from about 27 wt. %to about 23 wt. %, based on the total weight of the composition.Suitable elastomers and impact-modifying compatibilizer are commerciallyavailable from ExxonMobil Corporation under its Vistamaxx® brand, TheDOW Chemical Company under its Engage® brand, LyondellBasell Industriesunder its Catalloy® brand, Kraton Performance Polymer Inc., and MitsuiChemicals, Inc. under its Tafmer® brand.

III. Fillers

In some embodiments, the filler is present in an amount ranging fromabout 5 wt. % to about 12 wt. %, alternatively from about 6 wt. % toabout 11.4 wt. %, alternatively from about 8 wt. % to about 11.5 wt. %,and alternatively about 9 wt. %, where each range and percentage beingbased on the total weight of the composition. In some embodiments, thefiller may be a talc having a high aspect ratio, glass, glass bubbles,carbon fibers, mineral fibers, biofillers such as wood, flax, wheatstaw, coconut, kenaf, and hemp, and combinations thereof (such as talcwith glass bubbles or talc with carbon fibers).

IV. Additive Packages

In some embodiments, the additive package may comprise one or more ofthe following: antioxidant(s); mold release(s); scratch reductionadditive(s); nucleating agent(s); neutralizer(s)/acid scavenger(s)selected from the group consisting of magnesium aluminum hydroxylcarbonate and hydrates thereof; and stearic acid and/or a stearate salt.

In some embodiments, the additive package comprises an antioxidant,wherein the antioxidant is an organophosphite or a blend of more thanone organophosphite.

In some embodiments, the scratch reduction additive may includelubricants such as fatty amides; examples of which include oleamide(“OR”), ethylene bis-steramide (EBS), and/or erucamide, and the like.For example, the oleamide (OR) may be Crodamide® OR supplied by Croda;the erucamide (ER) may be Crodamide® ER supplied by Croda; and theethylene bis-steramide (EBS) may be Crodamide® EBS supplied by Croda.

In some embodiments, the mold release additive may include one or moreof glycerol monostearate, stearic acid, a stearate salt, magnesiumstearate, calcium stearate, and the like. See, for example, U.S. Pat.No. 3,886,105, which is incorporated herein by reference. Alternatively,magnesium stearate may be used as a dispersion aid.

In some embodiments, the additive package comprises a nucleating agent,wherein the nucleating agent is hexahydrophthalic acid, a salt thereof,or an anhydride thereof. In some embodiments, the nucleating agent is acalcium salt of hexahydrophtalic acid. See, for example, WIPO PCTApplication Publication No. WO 2008/073401, which is incorporated hereinby reference. In some embodiments, the nucleating agent is present in anamount ranging from about 0.05 wt. % to about 3 wt. %; alternativelyabout 0.1 wt. % to about 0.2 wt. %, based on the total weight of thecomposition. In some of these embodiments, the nucleating agent ispresent in an amount of about 0.15 wt. %, based on the total weight ofthe composition.

In some embodiments, the additive package comprises a neutralizer/acidscavenger, wherein the neutralizer/acid scavenger is magnesium aluminumhydroxy carbonate or hydrates thereof. Magnesium aluminum hydroxycarbonate hydrates are effective in retarding hindered amine lightstabilizer deactivation. One magnesium aluminum hydroxy carbonatehydrate for use with the present disclosure is sold under the trademark“DHT-4A or DHT-4V” by Kyowa Chemical Industry Co. Ltd.

In some embodiments, the additive package further comprises one or moreof the following type of substances: colorants, odorants, deodorants,plasticizers, impact modifiers, surfactants, wetting agents, flameretardants, ultraviolet light stabilizers, antioxidants, biocides, metaldeactivating agents, thickening agents, heat stabilizers, defoamingagents, coupling agents, polymer alloy compatibilizing agents, blowingagents, emulsifiers, crosslinking agents, waxes, particulates, flowpromoters, and other materials added to enhance processability orend-use properties of the polymeric components. Such additives may beused in conventional amounts. In some embodiments, the amounts do notexceed 10 weight percent (wt. %) of the total weight of the composition.

In some embodiments, the additives are added individually (or incombination) to the composition directly, optionally while thecomposition is being blended or extruded, such that the additives aredistributed approximately evenly throughout the composition. This typeof additive addition may be called a “salt and pepper addition.” Inother embodiments, the additives may be pre-blended into a polymercarrier. The polymer carrier may be a homopolymer of polyethylene orpolypropylene. The polymer carrier having entrained additives may bereferred to as a masterbatch. The masterbatch may be added while thecomposition is being blended or extruded such that the additives aredistributed approximately evenly throughout the composition. Optionally,the polymer carrier may be 0.5-2 wt. % of the total weight of thecomposition; alternatively, the polymer carrier may be about 1 weightpercent of the total weight of the composition. In still furtherembodiments, some of the additives may be added via a masterbatch routeand other additives may be added via a salt and pepper addition.

In yet another embodiment, multiple masterbatches may carry differentadditives. For example, a first masterbatch may carry a colorant and asecond masterbatch may carry the remainder of the additives. Inembodiments using multiple masterbatches, the polymer carrier of eachmasterbatch may be the same or different.

V. Molded Parts/Articles

In another aspect, there are provided articles of manufacture comprisingone or more of the compositions disclosed herein. In some embodiments,the article is a part of an automobile, such as a molded part but mayalso include water vessels, locomotives, recreational vehicles,airplanes and other products. In some embodiments, the molded part is abumper fascia, a bumper, a rocker, a cladding, a wheel flare, a doorpanel, or an instrument panel. In some embodiments, such molded partsmay be used to assist the automotive industry in their pursuit ofmanufacturing lower weight cars with improved fuel efficiency and loweremissions. In some embodiments, the molded parts disclosed hereinexhibit a property profile of current higher density compositions, e.g.,those used for current bumper fascia resins. Such properties include,for example, consistent shrinkage and CLTE properties, while exhibitinga reduced density. In contrast to other lower density compositions knownin the art, the compositions provided herein do not, in someembodiments, result in an increase in CLTE or shrinkage. In someembodiments, the compositions (resins) provided herein are compatiblewith existing tooling and would therefore not require any or onlylimited retooling expense. In some embodiments, the compositionsprovided herein contrast with other low density compositions by avoidingany increase in expansion/contraction gapping. The auto industry ispursuing reduced gapping for improved craftsmanship.

In some embodiments, the articles may include embedded colorants. Inalternative embodiments, the articles may be colored, painted, or sealedafter (or before) being molded. In further embodiments, the articles maybe coated with various materials to facilitate paintability. In stillfurther embodiments, the articles may be coated with a clear seal or wax(before, after, or instead of being painted). The clear seal, wax,and/or paint (alone or in combination) may protect the article fromelements such as sun, heat, wind, rain, road debris including dirt andbugs, tree pollen or sap, and/or bird droppings.

VI. Methods and Process

In another aspect, there are provided methods of making an injectionmolded part (e.g., of an automobile) comprising melt blending theconstituents (a), (b), (c), and (d):

-   -   (a) a polyolefin comprising polypropylene, a propylene-ethylene        block copolymer, or combinations thereof, wherein the polyolefin        is present in an amount ranging from about 53 wt. % to about 65        wt. %, based on a total weight of the composition;    -   (b) a first elastomer, a second elastomer, and an        impact-modifying compatibilizer, wherein the combined weight        percent of the first elastomer, the second elastomer, and the        impact-modifying compatibilizer ranges from about 27 wt. % to        about 32 wt. %, based on the total weight of the composition;    -   (c) a filler present in an amount ranging from about 5 wt. % to        about 12 wt. %, based on the total weight of the composition;        and    -   (d) an additive package present in an amount ranging from about        0.5 wt. % to about 5 wt. %, based on the total weight of the        composition, wherein the composition has a density ranging from        about 0.90 to about 1.00 g/cm³, an after-bake-mold-shrinkage        (0.5 hours, 120° C.) ranging from about 0.5 percent to about 0.9        percent, a coefficient of linear thermal expansion ranging from        about 1 to about 8 (10⁻⁵ mm/mm/° C.), and a flexural modulus        between about 1,200 MPa and about 2,500 MPa. In some        embodiments, the methods comprise pelletizing the melt blend to        form a plurality of pellets. In some embodiments, the methods        comprise injection molding the pelletized blend. In some        embodiments, the constituents are blended with an extruder such        as a high-intensity continuous mixer or an internal batch mixer        (Banbury mixer, or a twin-screw extruder).

VII. Definitions

In the present description, the term “α-olefin” or “alpha-olefin” meansan olefin of the general formula CH₂═CH—R, wherein R is a linear orbranched alkyl containing from 1 to 10 carbon atoms. The α-olefin can beselected, for example, from propylene, 1-butene, 1-pentene, 1-hexene,1-octene, 1-dodecene and the like.

In the present description, the term “elastomer” refers to polymercompounds having rubber-like properties and crystallinity in the rangeof from about 0 percent to about 20 percent. In some embodiments, thepolymer can have crystallinity in the range of from about 0 percent toabout 5 percent.

In the present description, the term “elastomeric ethylene copolymercomposition” refers to a composition made from and/or containing atleast one elastomeric ethylene copolymer.

In the present description, the term “heterophasic polypropylenecopolymer” refers to a copolymer (or rubber copolymer) prepared by thecopolymerization of ethylene and propylene dispersed into apolypropylene matrix. The polypropylene matrix may be a homopolymer or acopolymer.

In the present description, the term “homopolymer” and similar termsmean a polymer consisting solely or essentially of units derived from asingle kind of monomer, e.g., ethylene homopolymer is a polymercomprised solely or essentially of units derived from ethylene, andpropylene homopolymer is a polymer comprised solely or essentially ofunits derived from propylene, and the like.

In the present description, the term “impact-modifying compatibilizer”means a compound that synergistically interacts with the interface ofthe elastomeric ethylene copolymer composition and the polyolefin toimprove the properties of the overall composition. For the purposes ofthe present disclosure the term “impact-modifying compatibilizer”includes the styrene-ethylene-butylene-styrene (SEBS) rubber and theheterophasic polypropylene copolymer described above.

In the present description, the term “interpolymer” refers to a polymerprepared by the polymerization of at least two types of monomers orcomonomers. It includes, but is not limited to, copolymers (which canrefer to polymers prepared from two different types of monomers orcomonomers, although it can be used interchangeably with “interpolymer”to refer to polymers made from three or more different types of monomersor comonomers), terpolymers (which can refer to polymers prepared fromthree different types of monomers or comonomers), tetrapolymers (whichcan refer to polymers prepared from four different types of monomers orcomonomers), and the like.

In the present description, the terms “monomer” and “comonomer” are usedinterchangeably. The terms mean any compound with a polymerizable moietythat is added to a reactor in order to produce a polymer. In thoseinstances in which a polymer is described as comprising one or moremonomers, e.g., a polymer comprising propylene and ethylene, the polymercomprises units derived from the monomers, e.g., —CH₂—CH₂—, and not themonomer itself, e.g., CH₂═CH₂.

In the present description, the term “polymer” means a macromolecularcompound prepared by polymerizing monomers of the same or differenttype. The term “polymer” includes homopolymers, copolymers, terpolymers,interpolymers, and so on.

In the present description, the term “polymer composition” refers to acomposition made from and/or containing at least one polymer.

In the present description, the term “polyolefin” as used hereinincludes polymers such as polyethylene, polypropylene, polybutene, andethylene copolymers having at least about 50 percent by weight ofethylene polymerized with a lesser amount of a comonomer such as vinylacetate, and other polymeric resins within the “olefin” familyclassification.

Polyolefins may be made by a variety of processes including batch andcontinuous processes using single, staged or sequential reactors,slurry, solution, and fluidized bed processes and one or more catalystsincluding for example, heterogeneous and homogeneous systems andZiegler-Natta, Phillips, metallocene, single-site, and constrainedgeometry catalysts to produce polymers having different combinations ofproperties. Such polymers may be highly branched or substantially linearand the branching, dispersity and average molecular weight may varydepending upon the parameters and processes chosen for their manufacturein accordance with the teachings of the polymer arts.

In the present description, the term “room temperature” refers to atemperature around 23 degrees Celsius (unless it is defined differentlyin an ASTM, in which case “room temperature” means as it is definedwithin that ASTM for that particular test/procedure/method).

In the present description, the term “thermoplastic polymer” means apolymer that softens when exposed to heat and returns to its originalcondition when cooled to room temperature.

In the present description, the terms “Ziegler-Natta-catalyzed polymer”and “Z-N-catalyzed polymer” mean any polymer that is made in thepresence of a Ziegler-Natta catalyst.

VIII. Testing Methods

Melt mass flow rates (MFR) are given in gram/10 min and were measuredusing ASTM D1238, which is entitled “Test Method for Melt Flow Rates ofThermoplastics by Extrusion Plastometer,” under the conditions specifiedbelow. The term “ASTM D 1238” as used herein refers to a standard testmethod for determining melt flow rates of thermoplastics carried out byan extrusion plastometer. In general, this test method covers thedetermination of the rate of extrusion of molten thermoplastic resinsusing an extrusion plastometer. After a specified preheating time, resinis extruded through a die with a specified length and orifice diameterunder prescribed conditions of temperature, load, and piston position inthe barrel. This test method was approved on Aug. 1, 2013 and publishedin August 2013, the contents of which are incorporated herein byreference in its entirety. For the referenced ASTM standards, visit theASTM website, www.astm.org, or contact ASTM Customer Service atservice@astm.org.

Filler or ash content is given in % and measured using ASTM D5630, whichis entitled “Standard Test Method for Ash Content in Plastics.” The term“ASTM D5630” as used herein refers to a standard test method fordetermining the inorganic content of plastics by destructive ashingprocedures. This test method was approved on Apr. 1, 2013 and publishedin April 2013, the contents of which are incorporated herein byreference in its entirety. For the referenced ASTM standards, visit theASTM website, www.astm.org, or contact ASTM Customer Service atservice@astm.org.

Density is giving in g/cm³ and measured using ISO 1183-1, which isentitled “Plastics-Methods for Determining the Density of Non-CellularPlastics—Part 1: Immersion method, liquid pycnometer method andtitration method.” The term “ISO 1183-1” as used herein refers to thetest method published as the second edition dated May 15, 2012, thecontent of which are incorporated herein by reference in its entirety.

Flexural modulus (or “flex modulus”) is given in megapascals (MPa) andmeasured using ISO 178, which is entitled “Plastics—Determination offlexural properties.” The term “ISO 178” as used herein refers to thetest method published as the fifth edition dated Dec. 15, 2010, thecontent of which are incorporated herein by reference in its entirety.

Charpy notched impact strength (or “Notched Charpy Impact Strength”) isgiven in KJ/m² and measured using ISO 179-1, which is entitled“Plastics—Determination of Charpy impact properties. Part 1:Non-instrumented impact test.” The term “ISO 179” or “179-1” as usedherein refers to the test method published as the second edition datedJun. 15, 2010, the content of which are incorporated herein by referencein its entirety.

Multi-Axial Instrumented Impact (MAII) energy values are given in joules(J) and a percentage ductile failure mode is recorded, and measuredusing ASTM D3763, which is entitled “Standard Test Method for High SpeedPuncture Properties of Plastics Using Load and Displacement Sensors.”The term “ASTM D3763” as used herein refers to the test method wasapproved on Sep. 1, 2015 and published in September 2015, the contentsof which are incorporated herein by reference in its entirety. For thereferenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at service@astm.org.

The Coefficient of Linear Thermal Expansion (CLTE) as measured throughthermal mechanical analysis (TMA) of annealed test specimens cut frominjection molded plaques is given in (10E−5 mm/mm/° C.) as an average ofthree data points in the flow direction and three data points in thecross flow direction. Each data point is measured using ISO 11359-2,which is entitled “Plastics—Thermomechanical analysis (TMA)—Part 2:Determination of coefficient of linear thermal expansion and glasstransition temperature.” The term “ISO 11359-2” as used herein refers tothe test method published as the first edition dated Oct. 1, 1999, thecontent of which are incorporated herein by reference in its entirety.

The as-molded shrinkage may be measured by molding a 4×6×⅛ inch plaque,allowing the plaque to cool to room temperature and re-condition over 48hours, and measuring the average shrinkage utilizing a fixed gauge.

The after-bake-mold-shrinkage may be measured by heating a roomtemperature, molded 4×6×⅛ inch plaque to a set temperature of 120° C.for either an hour or a half hour (as indicated), and measuring theaverage shrinkage after it is returned to room temperature andre-conditioned (or allowed to stabilize by leaving it at roomtemperature and a controlled humidity for over 24 hours) utilizing afixed gauge.

The use of the word “a” or “an,” when used in conjunction with the term“comprising” in the claims and/or the specification, may mean “one,” butit is also consistent with the meaning of “one or more,” “at least one,”and “one or more than one.”

Throughout this application, the term “about” is used to indicate that avalue includes the variation of error for the device, the method beingemployed to determine the value, or the variation that exists among thestudies.

The terms “comprise,” “have” and “include” are open-ended linking verbs.Any forms or tenses of one or more of these verbs, such as “comprises,”“comprising,” “has,” “having,” “includes” and “including,” are alsoopen-ended. For example, any method that “comprises,” “has” or“includes” one or more steps is not limited to possessing only those oneor more steps and also covers other unlisted steps.

A “method” is a series of one or more steps undertaken that lead to afinal product, result or outcome. As used herein, the word “method” isused interchangeably with the word “process.”

The term “olefin” as used in this application refers to an alkenewherein at least one carbon-carbon double bond in the molecule is aterminal double bond. Some non-limiting examples of olefins includestyrene, ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, or dodecene.

The above definitions supersede any conflicting definition in anyreference that is incorporated by reference herein. The fact thatcertain terms are defined, however, should not be considered asindicative that any term that is undefined is indefinite. Rather, allterms used are believed to describe the appended claims in terms suchthat one of ordinary skill can appreciate.

EXAMPLES

The following examples are included to demonstrate embodiments of theappended claims. Those of skill in the art should appreciate that manychanges can be made in the specific embodiments which are disclosed andstill obtain a like or similar result without departing from the spiritand scope of the disclosure herein.

Examples 1-4 were prepared using the materials, in the weight percentagethat were based on the total composition weight, summarized in Table 1.

First, the additives (as indicated in Table 1) were mixed with less than1 weight percent of talc (based on the overall composition) in alow-speed-offline-ribbon blender. In an embodiment, the premixing mayenhance distribution of the additives and help prevent agglomerationsfrom forming with potentially tacky raw materials. Then the additiveblend, along with all other remaining ingredients, were loaded into amixing chamber of a Farrel F270 Banbury Mixer (at the same time) andprocessed per the processing conditions of Table 2.

The blended compositions of each of Examples 1-4 were withdrawn from theFarrel F270 Banbury Mixer to a dump extruder, extruded through a die andpelletized, and later tested in accordance with the various testingmethods of Table 3. The results of the tests are provided in Table 3.

TABLE 1 Example Example Example Example Category Raw Materials MFRCondition Density 1 (wt. %) 2 (wt. %) 3 (wt. %) 4 (wt. %) MasterbatchMasterbatch 3.5 230° C., 1 1 1 Carrier Carrier B  2.16 kg PolyolefinPolyolefin A (PP 120 230° C., 43.95 43.05 homopolymer)  2.16 kgPolyolefin B (PP 65 230° C., 58.35 54.35 homopolymer)  2.16 kgPolyolefin C (PP 2.5 230° C., 13.7 14.6 homopolymer)  2.16 kg PolyolefinD (PP 1800 230° C., 5 homopolymer)  2.16 kg Elastomers First Elastomer A0.8 190° C., 0.875 16.6 16 16 16.6 (ethyl ene-butene  2.16 kg copolymer)First Elastomer B 1.2 190° C., 0.862 8.55 8.55 (ethyl ene-butene  2.16kg copolymer) Second Elastomer A 13 190° C., 0.864 10.65(ethylene-octene  2.16 kg copolymer) Second Elastomer B 30 190° C.,0.870 10.65 (ethylene-octene  2.16 kg copolymer) Impact-Impact-modifying 22 230° C., 0.90  3 5 5 3 modifying compatibilizer A  5kg compatibilizer (SEBS) Filler High aspect ratio 9.25 9.25 9.25 9.25talc. <3.5 um median diameter and top cut around 10 um. AdditiveAntioxidant 0.30 0.30 0.30 0.30 Package Scratch aid 0.25 0.25 0.25 0.25Nucleator 0.15 0.15 0.15 0.15 Neutralizer 0.05 0.05 0.05 0.05 Dispersionaid 0.10 0.10 0.10 0.10 Colorant Carbon black 1 1 1 1 masterbatch withPE carrier

TABLE 2 Farrel F270 Banbury Mixer, 270 Liter, 4-wing rotor ProcessConditions - Banbury Hopper Dump Time(s) - 10 Pre-Mix Ram Pressure(Psi) - 0 Pre-Mix Time(s) - 7 Ram Pressure (Psi) - 65 Intermediate MixTemp (° F.) - 328 Intermediate Addition Time(s) - 4 Final Mix Temp (°F.) - 345 Final Amps - 800 Flop Time(s) - 8 Drop Door Time(s) - 6Chamber Temp (° F.) - 130 Rotor Temp (° F.) - 90 Rotor Speed (RPM) - 95Process Conditions - Extruder Output Rate (Lb/Hr) - 12,000 Ext Zone 1Temp (° F.) - 250 Ext Zone 2 Temp (° F.) - 375 Ext Zone 3 Temp (° F.) -425 Ext Zone 4 Temp (° F.) - 450 Ext Zone 5 Temp (° F.) - 450 ScreenChanger Temp (° F.) - 450 Screen Temp (° F.) - 450 Transition Temp (°F.) - 450 Die Temp (° F.) - 450 Water Temp (° F.) - 135 Screen Type -20/80

TABLE 3 Example Example Example Example Properties Method Units 1 2 3 4Melt Flow Rate ASTM D1238 g/10 min 21.8 25.4 31.3 25.3 (2.16 kg, 230°C.) Ash Content (800° ASTM D3651 % 9.25 9.3 9.3 9.29 C., 30 min) DensityISO 1183 g/cm³ 0.95 0.96 0.95 0.95 Tensile Stress Yield ISO 527-1,2 MPa23.4 22.9 23.2 22.5 Elongation at Yield ISO 527-1,2 % 8.9 7.8 7.1 9.9Elongation at Break ISO 527-1,2 % 360 270 70 500 MAII −30° C. 2.2 ASTMD3763 J % 24.7 J 23.9 J 31.3 J 21.0 J m/s, Energy at Peak 100% 100% 100%100% Load and % Ductile Ductile Ductile Ductile Ductility FlexuralModulus ISO 178 MPa 1790 1788 1787 1736 Chord (64 mm span, 2 mm/min) HDTat 1.8 MPa ISO 75 ° C. 52 53.2 52.3 48.4 Charpy 23° C. ISO 179 kJ/m² 4245 44 41 (Notched) Charpy 0° C. ISO 179 kJ/m² 29 22 15 23 (Notched)Charpy −40° C. ISO 179 kJ/m² 3.3 4.0 4.17 4.24 (Notched) AMMS (48 h)ISO-294-4 - % 6.62 6.54 6.53 5.68 modified by LYB as described aboveABMS (0.5 h/120° ISO-294-4 - % 8.07 7.91 8.02 7.41 C.) modified by LYBas described above CLTE (TMA), Flow ISO 11359-2 10⁻⁵ mm/ 6.47 6.33 6.416.24 (Annealed) mm/C CLTE (TMA), X- ISO 11359-2 10⁻⁵ mm/ 6.41 6.44 6.526.40 Flow (Annealed) mm/C

All of the compositions, articles of manufacture, and methods disclosedand claimed herein can be made and executed without undueexperimentation in light of the present disclosure. While thecompositions, articles of manufacture, and methods of this disclosurehave been described in terms of certain embodiments, it will be apparentto those of skill in the art that variations may be applied to thecompositions, articles of manufacture, and methods, as well as in thesteps or in the sequence of steps of the methods described hereinwithout departing from the concept, spirit, and scope of the appendedclaims.

REFERENCES

The following references, to the extent that they provide exemplaryprocedural or other details supplementary to those set forth herein, arespecifically incorporated herein by reference.

-   U.S. Pat. No. 3,886,105-   U.S. Pat. No. 5,589,555-   U.S. Pat. No. 6,084,042-   U.S. Patent Publication No. 2015/0045479-   WIPO PCT Application No. WO2008/073401-   WIPO PCT Application No. WO2009/045351-   Anderson, N. G., Practical Process Research & Development—A Guide    for Organic Chemists, 2^(nd) ed., Academic Press, New York, 2012.-   ASTM Standard D1238, “Test Method for Melt Flow Rates of    Thermoplastics by Extrusion Plastometer,” approved on Aug. 1, 2013.-   ASTM Standard D5630, “Standard Test Method for Ash Content in    Plastics,” approved on Apr. 1, 2013.-   ASTM Standard D3763, “Standard Test Method for High Speed Puncture    Properties of Plastics Using Load and Displacement Sensors,”    approved on Sep. 1, 2015.-   International Standard ISO 1183-1, “Plastics—Methods for Determining    the Density of Non-Cellular Plastics—Part 1: Immersion method,    liquid pycnometer method and titration method,” second edition, May    15, 2012.-   International Standard ISO 178, “Plastics—Determination of flexural    properties,” fifth edition, Dec. 15, 2010.-   International Standard ISO 179-1, “Plastics—Determination of Charpy    impact properties. Part 1: Non-instrumented impact test,” second    edition, Jun. 15, 2010.-   International Standard ISO 11359-2, “Plastics—Thermomechanical    analysis (TMA)—Part 2: Determination of coefficient of linear    thermal expansion and glass transition temperature,” first edition,    Oct. 1, 1999.

What is claimed is:
 1. A composition comprising: (a) a polyolefincomprising polypropylene, a propylene-ethylene block copolymer, orcombinations thereof, wherein the polyolefin is present in an amountranging from about 53 wt. % to about 65 wt. %, based on a total weightof the composition; (b) a first elastomer, a second elastomer, and animpact-modifying compatibilizer, wherein the combined weight percent ofthe first elastomer, the second elastomer, and the impact-modifyingcompatibilizer ranges from about 25 wt. % to about 34 wt. %, based onthe total weight of the composition wherein: (i) the first elastomercomprises an ethylene-based copolymer having a density from about 0.87g/cm³ to about 0.90 g/cm³, wherein the first elastomer is present in anamount ranging from about 10 wt. % to about 22 wt. %, based on the totalweight of the composition; (ii) the second elastomer comprises anethylene-based copolymer having a density from about 0.85 g/cm³ to about0.87 g/cm³, wherein the second elastomer is present in an amount rangingfrom about 4 wt. % to about 15 wt. %, based on the total weight of thecomposition; and (iii) the impact-modifying compatibilizer is present inan amount ranging from about 0.5 wt. % to about 8 wt. %, based on thetotal weight of the composition, and the impact-modifying compatibilizeris a styrene-ethylene-butylene-styrene (SEBS) rubber having a melt flowrate (MFR, ASTM D1238, 230° C., 5 kg) from about 15 g/10 min to about 30g/10 min or a heterophasic polypropylene copolymer having a melt flowrate (MFR, ASTM D1238, 230° C., 2.16 kg) from about 0.1 g/10 min toabout 1.5 g/10 min; (c) a filler present in an amount ranging from about5 wt. % to about 12 wt. %, based on the total weight of the composition;and (d) an additive package present in an amount ranging from about 0.5wt. % to about 5 wt. %, based on the total weight of the composition,wherein the additive package comprises a nucleating agent, wherein thenucleating agent is hexahydrophthalic acid, a salt thereof, or ananhydride thereof present in an amount ranging from about 0.05 wt. % toabout 3 wt. %, based on the total weight of the composition; wherein thecomposition has a density ranging from about 0.90 to about 1.00 g/cm³,an after-bake-mold-shrinkage (0.5 hours, 120° C.) ranging from about 0.5percent to about 0.9 percent, a coefficient of linear thermal expansionranging from about 1×10⁻⁵ mm/mm/° C. to about 8×10⁻⁵ mm/mm/° C., and aflexural modulus between about 1,200 MPa and about 2,500 MPa.
 2. Thecomposition of claim 1, wherein the ethylene-based copolymer of thefirst elastomer has a melt flow rate (MFR, ASTM D1238, 190° C., 2.16 kg)from about 0.4 g/10 min to about 1.1 g/10 min.
 3. The composition ofclaim 2, wherein the ethylene-based copolymer of the first elastomer isselected from an ethylene-butene copolymer, ethylene-hexene copolymer,and an ethylene-octene copolymer.
 4. The composition of claim 3, whereinthe ethylene-based copolymer of the first elastomer is anethylene-butene copolymer.
 5. The composition of claim 1, wherein theethylene-based copolymer of the second elastomer has a melt flow rate(MFR, ASTM D1238, 190° C., 2.16 kg) from about 1 g/10 min to about 1.5g/10 min.
 6. The composition of claim 1, wherein the ethylene-basedcopolymer of the second elastomer has a melt flow rate (MFR, ASTM D1238,190° C., 2.16 kg) from about 5 g/10 min to about 50 g/10 min.
 7. Thecomposition of claim 1, wherein the additive package comprises one ormore of the following: an antioxidant; a mold release; a scratchreduction additive; a nucleating agent; a neutralizer/acid scavengerselected from the group consisting of magnesium aluminumhydroxycarbonate and hydrates thereof; and stearic acid or a stearatesalt.
 8. The composition of claim 1, wherein the composition has a meltflow rate (MFR, ASTM D1238, 230° C., 2.16 kg) from about 15 g/10 min toabout 50 g/10 min.
 9. The composition of claim 1, wherein thecomposition has a density from about 0.90 g/cm³ to about 0.97 g/cm³. 10.The composition of claim 1, wherein the composition has a coefficient oflinear thermal expansion (CLTE) from about 5×10⁻⁵ mm/mm/° C. to about8×10⁻⁵ mm/mm/° C.
 11. The composition of claim 1, wherein thecomposition has a flex modulus greater than about 1,650 MPa and lessthan about 2,100 MPa.
 12. The composition of claim 1, further comprisingan as-molded shrinkage percentage of the composition is from about 0.5percent to about 0.8 percent.
 13. The composition of claim 12, whereinthe as-molded shrinkage percentage of the composition is about 0.6percent.
 14. The composition of claim 1, wherein the after-bake moldshrinkage percentage of the composition is from about 0.6 percent toabout 0.9 percent.
 15. An article formed from the composition ofclaim
 1. 16. The article of claim 15, wherein the article is a part ofan automobile.